Water soluble azo dyes containing a cyanoamino-triazinyl-amino group and a fiber-reactive of the sulfone series

ABSTRACT

Water-soluble azo dyes and their heavy metal complex derivatives, such as copper, cobalt and chromium complex azo dyes are described, which have the general formula (1) shown below, have fiber-reactive properties and dye natural and synthetic hydroxyl- and/or carboxamido-containing materials, in particular fiber materials, such as wool and in particular cellulose fiber materials, by the dyeing and printing processes customary for fiber-reactive dyes, in hues which have high color strength and good fastness properties. ##STR1##

The invention is in the technical field of fiber-reactive dyes.

Azo dyes containing a 2-chloro-4-cyanamido-s-triazin-6-ylamino radicalare known from U.S. Pat. No. 3,758,470. However, these known dyes havecertain shortcomings in practical application; thus, they are inparticular not suitable for dyeing by the cold pad-batch method and thevarious exhaust methods at lower dyeing temperatures (40° to 60° C.).

Furthermore, dyes are known from European Patent Application PublicationNo. 0,040,806A, which have a fiber-reactive radical of the vinyl sulfoneseries at a separate point of the chromophore, and which have as afurther fiber-reactive radical a fluoro-s-triazinylamino group, whichcontains as further substituents, inter alia, an optionally substitutedamino group. In Table Example 23 a monoazo dye is named which is said tocontain a 2-cyanamido-4-fluoro-s-triazin-6-ylamino group, whosesynthesis is however difficult.

By means of the present invention, new water-soluble azo dyes have nowbeen found which are improved in this respect and have the generalformula (1) ##STR2## in this formula, the symbols have the followingmeanings: F is the radical of a monoazo, disazo or polyazo dye or of aheavy metal complex azo dye, such as a 1: copper complex, 1:2 chromiumcomplex or 1:2 cobalt complex azo dye;

R is hydrogen or alkyl of 1 to 4 carbon atoms, such as methyl or ethyl,which can be substituted by halogen, such as chlorine and bromine,hydroxyl, cyano, alkoxy of 1 to 4 carbon atoms, such as methoxy andethoxy, alkoxycarbonyl of 2 to 5 carbon atoms, carboxyl, sulfamoyl,sulfo or sulfato, and is preferably methyl or ethyl and in particularhydrogen;

X is chlorine, bromine, sulfo, alkylsulfonyl of 1 to 4 carbon atoms orphenylsulfonyl, preferably chlorine;

Y is vinyl, β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl,β-alkanoyloxyethyl of 2 to 5 carbon atoms in the alkanoyl radical, suchas β-acetyloxyethyl, β-benzoyloxyethyl, β-(sulfobenzoyloxy)ethyl,β-(p-toluenesulfonyloxy)ethyl or β-halogenoethyl, such as β-bromoethylor β-chloroethyl, preferably vinyl and in particular β-sulfatoethyl;

p is the number 1 or 2;

n is the number 1 or 2, preferably 1.

The groups --SO₂ --Y can be bound to an aromatic carbon atom of F via analkylene radical of 1 to 4 carbon atoms, such as a methylene group, orvia an alkylamino group of 1 to 4 carbon atoms, such as a methylamino orethylamino group.

F is preferably the radical of a monoazo or disazo dye or the radical ofan o,o'-1:1 copper complex monoazo or disazo dye. The radical F cancontain the substituents customary for organic dyes, including afiber-reactive group of a type other than that shown in formula (1),bound to its basic structure. Examples of these substituents are: alkylgroups of 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropylor butyl, of these, preferably ethyl and in particular methyl; alkoxygroups of 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy,isopropoxy and butoxy, of these, preferably ethoxy and in particularmethoxy; acylamino groups of 2 to 8 carbon atoms, such as acetylamino,propionylamino or benzoylamino groups; primary and monosubstituted ordisubstituted amino groups, such as, for example, those substituted byalkyl groups of 1 to 4 carbon atoms and/or phenyl groups, such asmonoalkylamino and dialkylamino groups of 1 to 4 carbon atoms in thealkyl radical, phenylamino or N-(C₁ -C₄ -alkyl)-N-phenylamino groups, inwhich the alkyl radicals can be further substituted, for example byphenyl, sulfophenyl, hydroxyl, sulfato, sulfo and carboxyl, and thephenyl groups can be further substituted, such as by chlorine, sulfo,carboxyl, methyl and/or methoxy, for example methylamino, ethylamino,propylamino, isopropylamino, butylamino, N,N-di(β-hydroxyethyl)amino,N,N-di(β-sulfatoethyl)amino, sulfobenzylamino, N,N-di(sulfobenzyl)aminoand diethylamino groups and phenylamino and sulfophenylamino groups;alkoxycarbonyl groups having an alkyl radical of 1 to 4 carbon atoms,such as methoxycarbonyl and ethoxycarbonyl; alkylsulfonyl groups of 1 to4 carbon atoms, such as methylsulfonyl and ethylsulfonyl;trifluoromethyl, nitro and cyano groups; halogen atoms, such asfluorine, chlorine and bromine; carbamoyl groups, which can bemonosubstituted or disubstituted by alkyl of 1 to 4 carbon atoms, inwhich the alkyl radicals in turn can be substituted, such as, forexample, by hydroxyl, sulfato, sulfo, carboxyl, phenyl and sulfophenyl,such as, for example N-methylcarbamoyl and N-ethylcarbamoyl; sulfamoylgroups, which can be monosubstituted or disubstituted by alkyl groups of1 to 4 carbon atoms, and N-phenyl-N-alkylsulfamoyl groups having analkyl group of 1 to 4 carbon atoms, in which these alkyl groups in turncan be substituted by hydroxyl, sulfato, sulfo, carboxyl, phenyl andsulfophenyl, such as, for example, N-methylsulfamoyl, N-ethylsulfamoyl,N-propylsulfamoyl, N-isopropylsulfamoyl, N-butylsulfamoyl,N-(β-hydroxyethyl)sulfamoyl and N,N-di(β-hydroxyethyl)sulfamoyl;N-phenylsulfamoyl, ureido, hydroxyl, carboxyl, sulfomethyl and sulfogroups.

The dye radical F is preferably substituted by one or more, such as 2 to4, sulfo groups and furthermore can preferably contain substituentsselected from the group comprising methyl, ethyl, methoxy, ethoxy,acetylamino, benzoylamino, amino, chlorine, bromine, ureido, hydroxyl,carboxyl and sulfomethyl.

The dye radical F can also have other fiber-reactive groups known fromthe literature, which do not correspond to the formula --SO₂ --Y where Yhas the abovementioned meaning and not to the general formula (3)mentioned later. These known fiber-reactive groups are, for example, alow-molecular-weight alkanoylamino radical which is unsubstituted orsubstituted by a detachable atom or a detachable group, alow-molecular-weight alkenoylamino or alkenesulfonylamino radical, whichis unsubstituted or substituted by a detachable atom or a detachablegroup, or a carbocyclic, carbocyclicheterocyclic or heterocyclicradical, which is unsubstituted or substituted by a detachable atom or adetachable group, which are bound to the radical A via a carbonylaminoor sulfonylamino group and in which the heterocyclic components of theseradicals are four-, five- or six-membered, or a triazinyl or pyrimidinylradical, which is bound to the radical A via an amino, methylamino orethylamino group and is unsubstituted or substituted by a detachableatom or a detachable group. Examples of these radicals are ahalogen-substituted six-membered heterocyclic radical, bound via anamino, methylamino or ethylamino group, such as, for example, ahalogenotriazinyl or halogenopyrimidinyl radical, or are aliphaticacylamino radicals, such as a halogenoacetylamino orhalogenopropionylamino radical.

Examples of formula radicals R are: hydrogen, methyl, ethyl, propyl,isopropyl, butyl, isobutyl, sec.-butyl, tert.-butyl, carboxymethyl,β-carboxyethyl, β-carboxypropyt, methoxycarbonylmethyl,ethoxycarbonylmethyl, β-methoxyethyl, β-ethoxyethyl, β-methoxypropyl,β-chloroethyl, γ-bromopropyl, β-hydroxyethyl, β-hydroxybutyl,β-cyanoethyl, sulfomethyl, β-sulfoethyl, amidosulfonylmethyl andβ-sulfatoethyl.

Of the 1:1 copper complex azo dyes according to the invention, those ofthe benzene and naphthalene series are preferred.

Monoazo and disazo dyes according to the invention of the generalformula ( 1 ) are, for example, those of the general formula ( 2a ) or(2b)

    (Y--SO.sub.2).sub.p --D--N═N--(E--N═N).sub.v --K--Z(2 a)

    Z--D--N═N--(E--N═N).sub.v --K--(SO.sub.2 --Y).sub.p( 2b)

or of a heavy metal complex derived therefrom, such as a 1:1 coppercomplex, in which

Y and p have the abovementioned meanings,

D is the radical of a diazo component of the benzene or naphthaleneseries,

E is the radical of a middle component of the benzene or naphthaleneseries and

K is the radical of a coupling component of the benzene, naphthalene,pyrazolone, 6-hydroxy-2-pyridone or acetoacetarylamide series, in whichD, E and K can contain substituents customary for azo dyes, inparticular sulfo, carboxyl, hydroxyl, amino, methyl, ethyl, methoxy,ethoxy groups, substituted or unsubstituted alkanoylamino groups of 2 to4 carbon atoms in the alkanoyl radical, substituted or unsubstitutedbenzoylamino groups and halogen atoms, such as bromine and chlorineatoms, and/or a trifluoromethyl group, D, E and K together having atleast two sulfo groups, preferably three or four sulfo groups,

v is the number zero or 1 and

Z is a group of the formula (3) ##STR3## where R and X have theabovementioned meanings.

Further preferred disazo dyes are those of the general formula (2c)

    (Y--SO.sub.2).sub.p --D--N═N--K.sup.o --N═N--D--Z  (2c)

in which Y, p and Z have the abovementioned meanings and both D,independently of one another, are the radical of a diazo component ofthe benzene or naphthalene series and K^(o) is the radical of a bivalentcoupling component of the naphthalene series, it being possible for Dand K^(o) to carry the substituents customary for azo dyes, such assulfo, carboxyl, hydroxyl, amino, methyl, ethyl, trifluoromethyl,methoxy and ethoxy groups, substituted or unsubstituted alkanoylaminogroups of 2 to 4 carbon atoms in the alkanoyl radical, substituted orunsubstituted benzoylamino groups and halogen atoms, such as chlorineand bromine atoms, both D and K^(o) together containing at least twosulfo groups, preferably three or four sulfo groups.

Of the disazo compounds according to the invention of the generalformula (2c), especially those may be mentioned in particular which havethe general formula (2d) and (2e) ##STR4## in which M is hydrogen or analkali metal, such as sodium, potassium or lithium, and

D, Y and Z have the abovementioned meanings.

Examples of preferred metal complex azo dyes according to the inventionare those which have the general formula (2f) ##STR5## in which Z¹ is aradical of the general formula (3a) ##STR6## where X has theabovementioned, particularly preferred, meaning and D¹ has the meaninggiven below and Y, p, R¹, R², v and K have the abovementioned,particularly preferred, meanings,

in which both K as the radicals of a coupling component, independently oone another, are particularly preferably the radical of anaminosubstituted naphthol, which can be substituted by 1 or 2 sulfogroups.

Of the dyes according to the invention, those can furthermore bementioned as being preferred which have the general formulae (2A) to(2G): ##STR7## in which the symbols have the following meanings: M, Y,Z¹ and p have one of the abovementioned, in particular preferred,meanings;

R¹ is hydrogen, alkyl of 1 to 4 carbon atoms, such as ethyl and inparticular methyl, alkoxy of 1 to 4 carbon atoms, such as ethoxy and inparticular methoxy, halogen, such as chlorine and bromine,trifluoromethyl, carboxyl or sulfo;

R² is hydrogen, alkyl of 1 to 4 carbon atoms, such as ethyl and inparticular methyl, alkoxy of 1 to 4 carbon atoms, such as ethoxy and inparticular methoxy, halogen, such as chlorine and bromine, or sulfo;

D¹ is a benzene ring, or a naphthalene ring to which the azo group ispreferably bound in the β-position, and in the case where D is anaphthalene ring, R¹ and R² are each preferably, independently of oneanother, hydrogen or sulfo;

m is the number zero, 1 or 2 (this group being hydrogen in the casewhere m is zero);

R.sup. 3 is alkyl of 1 to 4 carbon atoms, such as ethyl or methyl;

R⁴ is methyl, carboxyl or carbalkoxy of 2 to 5 carbon atoms, such ascarbomethoxy;

the one --SO₃ M group bound in formula (2G) to the aminonaphthol radicalis preferably in the meta position relative to the amino group.

The present invention furthermore relates to a process for thepreparation of the dyes according to the invention of the generalformula (1). They can be prepared in a manner known per se analogouslyto known synthetic routes which are specific for the particular class ofdyes by reacting precursors which are representative of the particulardye, and at least one of which contains a 20 group of the generalformula (3) and at least one of which contains a group of the generalformula --SO₂ --Y, with one another or by starting with anamino-containing starting compound of the general formula (14) ##STR8##in which Y, p, F, R and n have the abovementioned meanings and reactingit with a halogeno-s-triazine of the general formula (15) ##STR9## inwhich Hal is a chlorine or bromine atom and X has the abovementionedmeaning and with cyanamide or an alkali metal salt thereof instoichiometric amounts in any desired order with one another and, ifdesired, subsequently carrying out further necessary conversionreactions known to one skilled in the art. These starting compounds,including the compounds of the general formula (14), have been describedin the literature in large numbers. The reaction can be carried outanalogously to the procedures known and customary in the literature ofthe reaction of a halogenotriazine with an amino compound and/or withcyanamide (see, for example, U.S. Pat. No. 3,758,470 mentioned at thebeginning).

The dyes according to the invention can in particular be preparedaccording to the invention by reacting a compound of the general formula(16) ##STR10## in which Y has the abovementioned meaning, but ispreferably a β-hydroxyethyl group, and in which p, F, R, X, Hal and nhave the abovementioned meanings, with cyanamide or an alkali metal saltthereof, or by reacting an amino compound of the general formula (14)with a compound of the general formula (17) ##STR11## in which X and Halhave the abovementioned meanings.

The azo compounds according to the invention can also be prepared inaccordance with the customary procedures of diazotization and couplingby starting with the diazo and coupling components suitable for theparticular dye, one component of which contains one or two groups of thegeneral formula --SO₂ --Y where Y has the abovementioned meaning and theother a radical of the general formula (3). Diazo components andcoupling components containing one or two groups of the formula --SO₂--Y or one group of the general formula (3) and their synthesis havealso been described in the literature.

The reaction of the starting compound of the general formula (16) withcyanamide or an alkali metal salt thereof is carried out in aqueousmedium, preferably in solution, at a temperature between 20° and 95° C.,preferably between 40° and 70° C., and at a pH between 7 and 12,preferably between 8 and 10.

The reaction of the starting compound of the general formula (14) withthe compound of the general formula (17) is carried out in aqueous oraqueous-organic medium in suspension or solution at a temperaturebetween 0° and 60° C., preferably between 15° and 30° C., and at a pHbetween 2 and 7, preferably between 3 and 4.5. The organic portion ofthe reaction medium is, for example, acetone, dimethylformamide orN-methylpyrrolidone.

Under certain reaction conditions, a halogenotriazine radical can inducehydrolysis; that is why in the case of an intermediate or precursorwhich contains a protective group, such as, for example, an acetylaminogroup, the acetyl group has to be cleaved off by hydrolysis before thereaction with the halogenotriazine can take place. The order in whichthe various abovementioned reactions between the halogenotriazine andthe amino starting compounds are advantageously carried out first, isdifferent from case to case and depends in particular on the solubilityof the amino compounds involved and the basicity of the amino groupswhich are to be reacted with the halogenotriazine radical.

The synthesis according to the invention by means of diazotization andcoupling reaction of the corresponding diazo and coupling startingcomponent is carried out by the usual procedure of diazotization andcoupling reactions, for example the diazotization, as a rule, at atemperature between -5° C. and +15° C. and a pH below 2 by means of astrong acid and alkali metal nitrite in, preferably, aqueous medium andthe coupling reaction, as a rule, at a pH between 1.5 and 4.5 in thecase of an amino-containing coupling component and at a pH between 3 and7.5 in the case of a hydroxyl-containing coupling component and at atemperature between 0° and 25° C., also preferably in aqueous medium.

The synthesis according to the invention of the heavy metal complex azodyes according to the invention can, for example, also be started withthose metal-free azo dyes which have the general formula (1), but inwhich the diazo and coupling components in the ortho position relativeto the azo group each contain a hydroxyl group or carboxyl group capableof forming a complex. This o,o'-dihydroxy- or o-carboxy-o'-hydroxyazostarting compound of the general formula (1) is then reacted in acustomary and known manner with an agent donating a heavy metal ion,such as, for example, copper chloride, copper sulfate, chromiumchloride, chromium sulfate and cobalt chloride to give the heavy metalcomplex azo dye according to the invention.

For example, the copper complex azo compounds according to the inventionof the general formula (2f) can be prepared in such a manner that acompound of the general formula (18) ##STR12## in which the individualformula members have one of the abovementioned meanings is reacted withan agent donating a copper ion, such as, for example, copper chloride orcopper sulfate, in aqueous medium at a temperature between 0° and 30° C.

As has already been indicated above the dyes according to the inventioncan also be prepared according to the invention by starting with acompound of the general formula (1) and the meanings mentioned, exceptthat the group(s ) --SO₂ --Y are β-hydroxyethylsulfonyl groups (thisstarting compound can be prepared analogously to the abovementionedprocedures according to the invention by starting from suitable startingcompounds having a β-hydroxyethylsulfonyl group) and converting in thisstarting compound of the formula (1) where Y is β-hydroxyethyl theβ-hydroxyethylsulfonyl groups into other groups --SO₂ --Y of thecompound (1) according to the invention in analogy to known proceduresaccording to the invention, for example into their ester derivatives,such as, for example, of polyhydric inorganic acids or of aliphatic andaromatic carboxylic or sulfonic acids, for example in compounds in whichY is a β-chloroethyl, β-sulfatoethyl, β-phosphatoethyl,β-thiosulfatoethyl, β-acetyloxyethyl or β-toluenesulfonyloxyethyl group.Examples of suitable esterification and acylating agents for thisreaction are the corresponding inorganic or organic acids, theiranhydrides or halides or amides, such as, for example, sulfuric acid,sulfuric acid containing sulfur trioxide, chlorosulfonic acid, sulfamicacid, phosphoric acid, polyphosphoric acid, phosphorus oxychloride,mixtures of phosphoric acid and phosphorus pentoxide, acetic anhydride,toluenesulfonyl chloride and thionyl chloride.

The sulfation is carried out, for example, by reaction with concentratedsulfuric acid at temperatures between 0° and 20° C. or by reaction withchlorosulfonic acid in a polar organic solvent, such as, for example,N-methylpyrrolidone at a temperature between 10° and 80° C. Preferably,the sulfation is carried out by adding the starting dye which containsβ-hydroxyethyl groups to sulfuric acid monohydrate at a temperaturebetween 5° and 15° C.

Those compounds in which Y is a vinyl group can be prepared from theiranalogous ester derivatives by means of alkali, for example in anaqueous medium at a pH of 10 to 12 and a temperature between 30° and 50°C. and a reaction time of 10 to 20 minutes. The synthesis of, forexample β-(dialkylamino)ethylsulfonyl and β-thiosulfatoethylsulfonylderivatives is carried out by reaction of their vinylsulfonyl compoundswith the corresponding dialkylamine or with an alkali metal salt ofthiosulfuric acid, such as sodium thiosulfate. All these procedures ofconverting a group --SO₂ --Y into another group are known to one skilledin this fiber-reactive area and have been described in large numbers inthe literature.

The starting compounds of the general formula (17) can be preparedaccordingly or analogously to the procedures in U.S. Pat. No. 3,758,470,mentioned at the beginning, the reaction taking place in aqueous oraqueous-organic medium in suspension or solution (the organic mediumbeing, for example, acetone, dimethylformamide and N-methylpyrrolidone).This condensation reaction is preferably carried out at a temperaturebetween -5° C. and +30° C., in particular between 0° and 5° C., and at apH between 7 and 12, in particular between 8 and 10.

The starting compounds, such as, for example, diazo components, couplingcomponents and triazines have been described in the literature in largenumbers.

Aromatic radicals D of the diazo components D--NH₂ which carry afiber-reactive group of the formula Y--SO₂ -- are, for example, those ofthe amines of the general formulae (4a) and (4b) ##STR13## in which p¹is a radical of the formula (5a) ##STR14## in which Y and p have theabovementioned meanings and r is the number zero, 1 or 2,

p² is hydrogen, methyl, ethyl, methoxy, ethoxy, alkanoyl of 2 to 5carbon atoms, such as acetyl and propionyl, cyano, carboxyl, sulfo,alkoxycarbonyl of 2 to 5 carbon atoms, carbamoyl, N--(C₁ -C₄ -alkyl )carbamoyl, fluorine, chlorine, bromine or trifluoromethyl,

p³ is hydrogen, methyl, ethyl, methoxy, ethoxy, cyano, carboxyl, sulfo,alkanoylamino of 2 to 5 carbon atoms, such as acetylamino,alkoxycarbonyl of 2 to 5 carbon atoms, carbamoyl, N--(C₁ -C₄-alkyl)carbamoyl, fluorine, chlorine, nitro, sulfamoyl, N--(C₁ -C₄-alkyl)sulfamoyl, alkylsulfonyl of 1 to 4 carbon atoms, phenylsulfonylor phenoxy,

in which the benzene ring in formula (4a) and (4b) can additionallycontain a hydroxy group in the ortho position relative to the aminogroup,

m is the number zero, 1 or 2 (in which this group, in the case where pequals zero, is a hydrogen atom) and

M has the abovementioned meaning.

Of these, p² is preferably hydrogen, methyl, methoxy, bromine, chlorine,carboxyl and sulfo and p3 is hydrogen, methyl, methoxy, chlorine,carboxyl, sulfo and acetylamino.

The groups "sulfo" "carboxyl" "phosphato" "thiosulfato" and "sulfato"include their acid form as well as their salt form. Accordingly, sulfogroups are groups corresponding to the general formula --SO₃ M, carboxylgroups are groups corresponding to the general formula --COOM, phosphatogroups are groups corresponding to the general formula --OPO₃ M₂,thiosulfato groups are groups corresponding to the general formula--S--SO₃ M and sulfato groups are groups corresponding to the generalformula --OSO₃ M, where M has in each case the abovementioned meaning.

Aromatic amines of the diazo component Z--D--NH₂ containing thefiber-reactive radical Z are preferably derived from aromatic amines ofthe general formulae (4c) and (4d) ##STR15## in which R, M, m, p² and p³have the abovementioned, in particular preferred, meanings, in which thebenzene ring in formulae (4c) and (4d) can additionally contain ahydroxyl group in the ortho position relative to the amino group --NH₂.

Diamino starting compounds such as those of the formulae (4c) and (4d),which can be used as diazo components for the synthesis of the azocompounds according to the invention, are, for example:1,3-diaminobenzene, 1,4-diaminobenzene, 1,3-diamino-4-chlorobenzene,1,3-diamino-4-methylbenzene, 1,3-diamino-4-ethylbenzene,1,3-diamino-4-methoxybenzene, 1,3-diamino-4-ethoxybenzene,1,4-diamino-2-methylbenzene, 1,4-diamino-2-methoxybenzene,1,4-diamino-2-ethoxybenzene, 1,4-diamino-2-chlorobenzene,1,4-diamino-2,5-dimethylbenzene, 1,4-diamino-2,5-diethylbenzene,1,4-diamino-2-methyl-5-methoxybenzene, 1,4-diamino-2,5-dimethoxybenzene,1,4-diamino-2,5-diethoxybenzene, 2,6-diaminonaphthalene,1,4-diamino-naphthalene-2-sulfonic acid,2,6-diaminonaphthalene-8-sulfonic acid,2,6-diaminonaphthalene-4,8-disulfonic acid,1,4-diaminonaphthalene-6-sulfonic acid,1,3-diamino-2,4,6-trimethylbenzene,1,4-diamino-2,3,5,6-tetramethylbenzene, 1,3-diamino-4-nitrobenzene,4,4'-diaminostilbene, 4,4'-diaminodiphenylmethane, 4,4'-diaminobiphenyl(benzidine), 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine,3,3'-dichlorobenzidine, 3,3'-dicarboxybenzidine,3,3'-dicarboxymethoxybenzidine, 2,2'-dimethylbenzidine,4,2'-diaminodiphenyl (diphenyline),2,6-diaminonaphthalene-4,8-disulfonic acid,1,4-diaminobenzene-2-sulfonic acid, 1,4-diaminobenzene-2-carboxylicacid, 1,4-diaminobenzene-2,5-disulfonic acid,1,3-diaminobenzene-4-carboxylic acid, 1,2-diaminobenzene-4-carboxylicacid, 1,3-diaminobenzene-5-carboxylic acid, 1,4-diamino-2-methylbenzene,1,4-diaminobenzene-2,6-disulfonic acid, 1,3-diaminobenzene-4-sulfonicacid, 1,3-diaminobenzene-4,6-disulfonic acid,1,4-diamino-2-chlorobenzene-5-sulfonic acid,1,4-diamino-2-methylbenzene-5sulfonic acid,1,5-diamino-6-methylbenzene-3-sulfonic acid,1,3-diamino-6-methylbenzene-4-sulfonic acid,3-(3'-aminobenzoylamino)-1-aminobenzene-6-sulfonic acid,3-(4'-aminobenzoylamino)-1-aminobenzene-6-sulfonic acid,1-(4'-aminobenzoylamino)-4-aminobenzene-2,5-disulfonic acid,4,4'-diaminodiphenyl oxide, 4,4'-diaminodiphenylurea-2,2'-disulfonicacid, 4,4'-diaminodiphenyloxyethane-2,2'-disulfonic acid,4,4'-diaminostilbene-2,2'-disulfonic acid,4,4'-diaminodiphenylethane-2,2'-disulfonic acid,2-amino-5-aminomethylnaphthalene-l-sulfonic acid,2-amino-5-aminomethylnaphthalene-1,7-disulfonic acid.

If in the synthesis according to the invention, as mentioned above, anaminoalkanoylamino compound from which the alkanoyl group, such as, forexample, the acetyl group, is cleaved off again afterwards by hydrolysisis used as diazo component instead of a diamine, the monoalkanoylcompounds of the abovementioned diazo components are suitable, such as,for example, 1-acetylamino-3-aminobenzene-4-sulfonic acid and1-acetylamino-4-aminobenzene-3-sulfonic acid.

Starting amines containing a group Y--SO₂ --, such as, for example,those of the formulae (4a) and (4b), are, forexample,2-(β-sulfatoethylsulfonyl)aniline,3-(β-sulfatoethylsulfonyl)aniline, 4-(β-sulfatoethylsulfonyl)aniline,2-carboxy-5-(β-sulfatoethylsulfonyl)aniline,2-chloro-3-(β-sulfatoethylsulfonyl)aniline,2-chloro-4-(β-sulfatoethylsulfonyl)aniline, 2-ethoxy-4- or-5-(β-sulfatoethylsulfonyl)aniline,2-ethyl-4-(β-sulfatoethylsulfonyl)aniline, 2-methoxy-5-(β-sulfatoethylsulfonyl) aniline,2,4-diethoxy-5-(β-sulfatoethylsulfonyl)aniline,2,4-dimethoxy-5-(β-sulfatoethylsulfonyl) aniline, 2,5-dimethoxy-4-(β-sulfatoethylsulfonyl) aniline, 2-methoxy-5-methyl-4-(β-sulfatoethylsulfonyl) aniline, 2- or 3- or 4-(β-thiosulfatoethylsulfonyl)aniline,2-methoxy-5-(β-thiosulfatoethylsulfonyl)aniline,2-sulfo-4-(β-phosphatoethylsulfonyl)aniline,2-sulfo-4-vinylsulfonylaniline, 2-hydroxy-4- or-5-(β-sulfatoethylsulfonyl)aniline, 2-chloro-4- or-5-(β-chloroethylsulfonyl)aniline,2-hydrory-3-sulfo-5-(β-sulfatoethylsulfonyl) aniline, 3- or4-(β-acetoxyethylsulfonyl)aniline,2-methoxy-4-[β-(N-methyltauryl)-ethylsulfonyl]aniline,5-(β-sulfatoethylsulfonyl)-2-aminonaphthalene, 6- or 7- or8-(β-sulfatoethylsulfonyl)-2-aminonaphthalene,6-(β-sulfatoethylsulfonyl)-1-sulfo-2-aminonaphthalene, 5-(β-sulfatoethylsulfonyl)-1-sulfo-2-aminonaphthalene,8-(β-sulfatoethylsulfonyl)-6-sulfo-2-aminonaphthalene.

Preferred radicals D or D¹ in the formulae (2) and (4) containing afiber-reactive group Y--SO₂ -- or Z, are those of the general formulae(6a) to (6d): ##STR16## in which p¹, p², p³, Z, m and M have theabovementioned meanings.

Aromatic radicals E of a coupleable and diazotizable compound of thegeneral formula H--E--NH₂ are, for example, those of the generalformulae (7a ), (7b) and (7c) ##STR17## in which p², M and m have theabovementioned meanings and

p⁴ is hydrogen, alkyl of 1 to 4 carbon atoms, such as methyl or ethyl,alkoxy of 1 to 4 carbon atoms, such as methoxy and ethoxy, chlorine,alkanoylamino of 2 to 5 carbon atoms, such as acetylamino andpropionylamino, benzoylamino, ureido, phenylureido, alkylureido of 1 to4 carbon atoms in the alkyl radical, phenylsulfonyl or alkylsulfonyl of1 to 4 carbon atoms.

Compounds of the general formula H--E-NH₂ are, for example, aniline,3-methylaniline, 3-chloroaniline, 2,5-dimethylaniline,2,5-dimethoxyaniline, 3-methoxyaniline, 3-methyl-6-methoxyaniline,3-aminophenylurea, 3-acetylamino-6-methylaniline,2-amino-4-acetylaminobenzene-1-sulfonic acid, 1-aminonaphthalene,1-aminonaphthalene-6-or -7- or -8-sulfonic acid, 3-acetylaminoaniline,2-methylaniline, 2-methoxyaniline, 3-benzoylaminoaniline,2,3-dimethylaniline, 3,5-dimethylaniline,1-amino-2-methoxy-5-acetylaminobenzene, 3-propionylaminoaniline,3-butyrylaminoaniline, 2-sulfo-5-acetylaminoaniline,2-amino-5-naphthol-7-sulfonic acid and 2-amino-8-naphthol-6-sulfonicacid.

The radicals K of the coupling component are preferably derived from theaniline, naphthalene, pyrazole and acylacetarylide series; they cancontain fiber-reactive groups.

Coupling components of the formula H-K of the aniline and naphthaleneseries are, for example, the anilines, N- mono- and N,N-disubstitutedanilines, m-phenylenediamines and their derivatives, naphtholsulfonicacids, aminonaphthalenes, naphthols, hydroxynaphthoic acid derivatives,aminonaphthalenesulfonic acids or aminonaphtholsulfonic acids.

Coupling components of the formula H--K--(SO₂ --Y)_(p) are, for example,compounds of the general formulae (8a) to (8f) ##STR18## in which p²,p³, m and M have the abovementioned meanings,

p* is a radical of the formula (--SO₂ --Y)_(p) where Y and p have theabovementioned, in particular preferred, meaning or is a radical of theformula (5b) ##STR19## in which R* is methyl or ethyl,

w is the number zero or 1 and

Y has the abovementioned meaning,

p⁵ is phenylureido which is substituted in the phenyl radical bychlorine, methyl, methoxy, sulfo and/or carboxyl and by a group --SO₂--Y where Y has the abovementioned meaning, or is benzoylamino which issubstituted in the benzene radical by chlorine, methyl, methoxy, nitro,sulfo and/or carboxyl and by a group --SO₂ --Y where Y has theabovementioned meaning,

p⁶ is hydrogen, alkyl of 1 to 4 carbon atoms, such as methyl and ethyl,alkoxy of 1 to 4 carbon atoms, such as methoxy and ethoxy, bromine,chlorine or alkanoylamino of 2 to 7 carbon atoms, such as acetylaminoand propionylamino,

p⁷ is hydrogen, alkyl of 1 to 4 carbon atoms, such as methyl and ethyl,alkoxy of 1 to 4 carbon atoms, such as methoxy and ethoxy, chlorine oralkanoylamino of 2 to 7 carbon atoms, such as acetylamino andpropionylamino, ureido or phenylureido,

p⁸ is hydrogen or alkyl of 1 to 4 carbon atoms, which can be substitutedby hydroxy, cyano, carboxyl, sulfo, sulfato, methoxycarbonyl,ethoxycarbonyl or acetoxy or a group --SO₂ --Y of the above definition,

p⁹ is alkyl of 1 to 4 carbon atoms, which can be substituted byhydroxyl, cyano, carboxyl, sulfo, sulfato, methoxycarbonyl,ethoxycarbonyl or acetoxy and is substituted by a group --SO₂ --Y of theabove definition, or is benzyl or phenyl or phenyl which is substitutedby alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorineand/or sulfo, the phenyl radical being substituted by a group --SO₂ --Yof the above definition,

p¹⁰ is hydrogen, alkyl of 1 to 4 carbon atoms, such as methyl, cyano,carboxyl, carbalkoxy of 2 to 5 carbon atoms, such as carbomethoxy andcarbethoxy, carbamoyl or phenyl, preferably methyl, carboxyl,methoxycarbonyl, ethoxycarbonyl or phenyl and in particular methyl orcarboxyl, and

T is a benzene or naphthalene ring, preferably a benzene ring.

Compounds of the general formula (8) are, for example, 1-[3'-(β-chloroethylsulfonyl) benzoylamino]-3,6-disulfo-8naphthol,1-[3'-(vinylsulfonyl)benzoylamino]-3,6-disulfo-8-naphthol,1-[3'-(vinylsulfonyl)benzoylamino]-4,6-disulfo-8-naphthol,1-[3'-(β-sulfatoethylsulfonyl)benzoylamino]-4,6-disulfo-8-naphthol,2-[3'-(β-chloroethylsulfonyl)benzoylamino]-6-sulfo-8-naphthol,2-[3'-(vinylsulfonyl)benzoylamino]-6-sulfo-8-naphthol,3-[3'-(β-chloroethylsulfonyl)benzoylamino]-6-sulfo-8-naphthol,3-[3'-(vinylsulfonyl)benzoylamino]-6-sulfo-8-naphthol,2-[N-methyl-N-(β-sulfatoethylsulfonyl) amino]-6-sulfo-8-naphthol,3-[N-methyl-N-(β-sulfatoethylsulfonyl)amino]-6-sulfo-8-naphthol,2-[N-ethyl-N-(β-sulfatoethylsulfonyl)amino]-6-sulfo-8-naphthol,1-[N'-(3'-β-chloroethylsulfonylphenyl)ureido]-3,6-disulfo-8-naphthol,1-[N'-(3'-vinylsulfonylphenyl)ureido]-3,6-disulfo-8-naphthol,1-[N'-(3'-vinylsulfonylpropyl)ureido]-3,6-disulfo-8-naphthol,1-[N'-(3'-β-chloroethylsulfonylphenyl)ureido]-4,6-disulfo-8-naphthol,1-[N'-(3'-vinylsulfonylphenyl)ureido]-4,6-disulfo-8-naphthol,1-[N'-(3'-chloroethylsulfonylpropyl)ureido]-4,6-disulfo-8-naphthol,2-[N'-(3'-β-sulfatoethylsulfonylphenyl)ureido]-6-sulfo-8 -naphthol,2-[N'-(3'-β-chloroethylsulfonylpropyl)ureido]-6-sulfo-8-naphthol,3-[N'-(3'-β-chloroethylsulfonylphenyl) ureido]-6-sulfo-8-naphthol,3-[N'-(3'-vinylsulfonylpropyl) ureido]-6-sulfo-8-naphthol,1-[4'-(β-sulfatoethylsulfonyl) -2'-sulfo]phenyl-3-methylpyrazol-5-one,1-[4'-(β-sulfatoethylsulfonyl)phenyl]-3-carboxypyrazol-5-one,1-[4'-(β-sulfatoethylsulfonyl)phenyl]-3-methylpyrazol-5-one,1-[3'-(β-sulfatoethylsulfonyl)phenyl]-3-carboxypyrazol-5-one,1-[3'-(β-sulfatoethylsulfonyl)phenyl]-3-methylpyrazol-5-one,1-(4'-sulfophenyl)-3-carboxypyrazol-5-one,1-(4'-β-sulfatoethylsulfonylphenyl) -3-carbomethoxy-5-pyrazolone,1-(3'-β-sulfatoethylsulfonyl-phenyl) -3-carbomethoxy-5-pyrazolone,4-hydroxy-6-[N-methyl-N-(β-sulfatoethylsulfonyl)amino]naphthalene-2-sulfonicacid,4-hydroxy-6-[N-ethyl-N-(β-sulfatoethylsulfonyl)amino]naphthalene-2-sulfonicacid, 4-hydroxy-7-[N-methyl-N-(β-sulfatoethylsulfonyl)amino]naphthalene-2-sulfonic acid,4-hydroxy-7-[N-ethyl-N-(β-sulfatoethylsulfonyl)amino]naphthalene-2-sulfonicacid and acetoacetyl-(4-β-sulfatoethylsulfonyl) aniline. Furthersuitable coupling components H--K are in particular:1-amino-8-hydroxynaphthalene-3,6- and [lacuna]4,6-disulfonic acid andtheir arylazo coupling products obtained by acid coupling of the formula(9a) ##STR20## in which D¹ is a radical of the formula (10a), (10b) or(10c) ##STR21## in which R, p¹, p², p³, m and M have the abovementionedmeanings and Z¹ is a radical of the general formula (3a) shown below.

Coupling components which, according to the invention, contain thefiber-reactive group of the formula (3) or into which the fiber-reactivegroup can be introduced, if desired even after the coupling reaction,are, for example, compounds of the general formulae (11a) to (11h) ortheir Z.sup. -free precursors (i.e. compounds containing the group--N(R)--H instead of the group --N(R)--Z¹): ##STR22## in which R R, p²,p³, p¹⁰, p¹², p¹³, D², M, m and T have the abovementioned, in particularpreferred, meanings,

D² is a radical of the abovementioned general formula (10c),

B is alkyl of 1 to 4 carbon atoms, benzyl or phenethyl or phenyl, orbenzyl, phenethyl or phenyl which is substituted in the benzene radicalby fluorine, chlorine, bromine, methyl, methoxy, cyano, sulfo, carboxyl,acetyl, nitro, carbamoyl and/or sulfamoyl, in which in the case of"benzyl" and "phenethyl" the group --N(R^(x))--Z¹ is bound to thebenzene ring, and

Z¹ is a group of the general formula (3a) ##STR23## where X has one ofthe abovementioned meanings.

Those coupling components which contain a group of the general formula--NHR defined above or their alkanoyl derivative, the alkanoyl group ofwhich can, if desired or required, subsequently be cleaved offhydrolytically, are, for example: aniline, 3-methylaniline,3-chloroaniline, 2,5-dimethyl-aniline, 2,5-dimethoxyaniline,3-methoxyaniline, 3-methyl-6-methoxyaniline, 3-aminophenylurea,3-acetyl-amino-6-methylaniline, 2-amino-4-acetylaminobenzene-1-sulfonicacid, 1-aminonaphthalene, 1-aminonaphthalene-6-or -7- or -8-sulfonicacid, 3-acetylaminoaniline, 2-methylaniline, 2-methoxyaniline,3-benzoylaminoaniline, 2,3-dimethylaniline, 3,5-dimethylaniline,1-amino-2-methoxy-5-acetylaminobenzene, 4-(phenylazo)aniline,3-propionylaminoaniline, 3-butyrylaminoaniline,2-sulfo-5-acetylaminoaniline, 2-amino-5-naphthol-7-sulfonic acid,2-amino-8-naphthol-6-sulfonic acid, 6-methylamino-3-sulfo-1-naphthol,1-amino-3,6- or -4,6-disulfo-8-naphthol, 6-amino-3,5-disulfo-l-naphthol,6-(4'-aminophenyl)amino-3-sulfo-1-naphthol,1-amino-2,4-disulfo-8-naphthol,1-(4'-aminobenzoylamino)-3,6-disulfo-8-naphthol,1-(3'-aminobenzoylamino) -3,6-disulfo-8-naphthol,1-(4'-amino-2'-sulfophenyl) -3-carboxy-5-pyrazolone,1-(4'-amino-2'-sulfophenyl) -3-methyl-5-pyrazolone,1-(3'-sulfo-6'-methyl-5'-aminophenyl) -3-carboxy-5-pyrazolone,1-{4'-[N'-(4"-sulfo-3"-aminophenyl)carbamoyl]phenyl}-3-methyl- or -3-carboxy-5-pyrazolone, N-(3,5-disulfo-4-amino)acetoacetylanilide,N-(3-sulfo-4-amino-6-methoxy)acetoacetylanilide,2-hydroxy-5-carbamoyl-4-methyl-l-(β-aminoethyl)-6-pyridone and2-hydroxy-5-sulfomethyl-4-methyl-l-(β-aminoethyl)-6-pyridone,1-amino-8-hydroxynaphthalene-4sulfonic acid,1-amino-8-hydroxynaphthalene-6-sulfonic acid,1-amino-8-hydroxynaphthalene-2,4-disulfonic acid,2-hydroxy-3-aminonaphthalene-5,7-disulfonic acid,amino-8-hydroxynaphthalene-2,4,6-trisulfonic acid,hydroxy-8-acetylaminonaphthalene-3-sulfonic acid,amino-5-hydroxynaphthalene-7-sulfonic acid, 2-methyl- and2-ethylamino-5-hydroxynaphthalene-7-sulfonic acid,2-(N-acetyl-N-methylamino) -5-hydroxynaphthalene-7-sulfonic acid,2-acetylamino-5-hydroxynaphthalene-7-sulfonic acid,2-amino-5-hydroxynaphthalene-1,7-disulfonic acid,2-amino-8-hydroxynaphthalene-6-sulfonic acid, 2-methylamino- or2-ethylamino-8-hydroxynaphthalene-6-sulfonic acid,2-(N-acetyl-N-methylamino-8-hydroxynaphthalene-6-sulfonic acid,2-acetylamino-8-hydroxynaphthalene-6-sulfonic acid,2-amino-8-hydroxynaphthalene-3,6-disulfonic acid,2-acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid,1-amino-5-hydroxynaphthalene-7-sulfonic acid,1-amino-8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid,1-acetylamino-8-hydroxynaphthalene-3,6or -4,6-disulfonic acid,2-(4'-amino-3'-sulfophenylamino)-5-hydroxynaphthalene -7-sulfonic acid,1-(3'-aminophenyl) -3-methyl-5-pyrazolone,2,4,6-triamino-3-cyanopyridine,1-amino-8-hydroxy-2-(4'-sulfophenylazo)naphthalene-3,6-disulfonic acid,1-amino-8-hydroxy-2-(2',5'-disulfonephenylazo)naphthalene-3,6-disulfonic acid [sic],1-(β-aminoethyl)-3-cyano-4-methyl-6-hydroxy-2-pyridone,1-(7-aminopropyl)-3-sulfomethyl-4-methyl-6-hydroxy-2-pyridone,1,3-diaminobenzene, 1-amino-3--N,N-di(β-hydroxyethyl)aminobenzene,1-amino-3--N,N-di(β-sulfatoethyl)aminobenzene,1-amino-3--N,N-di(β-hydroxyethyl) amino-4-methoxybenzene,1-amino-3--N,N-di(β-sulfatoethyl) -amino-4-methoxybenzene,1-amino-3-sulfobenzylaminobenzene,1-amino-3-sulfobenzylamino-4-chlorobenzene,1-amino-3--N,N-di(sulfobenzyl)aminobenzene.

Aromatic diamines derived from the radical of the formula (10c) are, forexample, those which have the abovementioned formula (4c) and have beenmentioned there, for example, individually.

The compounds of the general formulae (11b) and (11c) themselves cannotbe used as coupling components. The coupling components which serve forthe synthesis of the azo dyes according to the invention are their Z¹-free precursors, i.e. their precursors which contain an amino group ofthe formula --N(R)--H instead of the group --N(R)--Z¹. After couplingthese amino-containing precursors onto a suitable diazo component togive the azo compound, the fiber-reactive radical Z¹ can be introducedinto the amino group --N(R)--H by means of a compound of the generalformula Hal--Z¹, in which Hal is a halogen atom, preferably a fluorineor chlorine atom, and Z¹ has the abovementioned meaning. Analogously,the Z¹ -free amino compounds of the compounds of the general formulae(11a) and (11d) to (11h) themselves can also first serve as couplingcomponents to prepare an aminoazo starting compound, into which thefiber-reactive radical can then be introduced in the same manner. Thecoupling components containing the fiber-reactive radical Z¹ of thegeneral formulae (11a) and (11d) to (11h) themselves can also beprepared by reaction of these Z¹ -free amino-containing startingcompounds with a compound of the formula Hal--Z¹ analogously to knownprocedures.

Instead of the radical Z¹, other known fiber-reactive radicals canlikewise be introduced into the amino groups of the amino-containingcoupling components or their aminoazo starting compounds, if those azodyes according to the invention in which the diazo component containsthe fiber-reactive grouping Z according to the invention are intended tobe prepared. In principle, all known fiber-reactive acylating agents aresuitable for this reaction.

Radicals K in the general formulae (2a) and (2b) which contain afiber-reactive group --SO₂ --Y are in particular radicals of the generalformulae (12a) to (12h) ##STR24## in which the individual formulamembers have the abovementioned meanings.

Radicals K in the general formulae (2a) and (2f) which contain the groupZ are in particular radicals of the general formula (12j) to (12p)##STR25## in which the individual formula members have theabovementioned meanings.

Radicals K of the general formula (2f) which contain an oxygen atombound to a metal complex and contain a fiber-reactive group --SO₂ --Y orZ (where v is zero) are in particular those of the formulae (13a) to(13f) ##STR26## in which Z^(*) has one of the meanings of P¹ or Z andthe individual formula members have one of the abovementioned meanings.

Radicals K in the general formula (2f) which contain an oxygen atombound to a metal complex in the case where v is 1 are in particularthose of the formulae (13g) and (13h) ##STR27## in which the individualformula members have one of the abovementioned meanings.

Halogenotriazine compounds of the general formula (13) are, for example,2,4,6-trichloro-1,3,5-triazine (cyanuric chloride),2,4,6-tribromo-1,3,5-triazine (cyanuric bromide),2-methylsulfonyl-4,6-dichloro-1,3,5-triazine and2-phenylsulfonyl-4,6-dichloro-1,3,5-triazine.

In all of the above formulae, the individual formula members, whetherthey have the same or different designation within a general formula,can, as far as their meaning is concerned, have meanings which areidentical to one another or different from one another.

The dyes according to the invention of the formula (1) are suitable forthe dyeing and printing of a wide range of materials, such as silk,leather, wool, polyamide fibers and polyurethanes, and in particularcellulose-containing fiber materials of any type. Examples of thesefiber materials are natural cellulose fibers, such as cotton, linen andhemp, and cellulose and regenerated cellulose. The dyes of the formula(1) are also suitable for the dyeing or printing of hydroxyl-containingfibers which are contained in mixed fabrics, for example of mixtures ofcotton with polyester fibers or polyamide fibers.

The dyes according to the invention can be applied to the fiber materialand fixed on the fiber by various methods, in particular in the form ofaqueous dye solutions and color print pastes. They are suitable not onlyfor the exhaust process but also for dyeing by the padding method, inwhich the material is impregnated with aqueous dye solutions which maycontain salts and the dye is fixed after an alkali treatment or in thepresence of alkali, if necessary with exposure to heat. The dyesaccording to the invention are particularly suitable for the coldpad-batch method, in which the dye is applied together with alkali on apad-mangle and is then fixed leaving it at room temperature for severalhours. After fixing, the dyes or prints are thoroughly rinsed witch coldand hot water, if necessary with the addition of an agent which acts asa dispersant and promotes the diffusion of the unfixed portions.

The present invention accordingly also relates to the use of thecompounds according to the invention of the general formula (1) for thedyeing (including printing) of these materials and to processes for thedyeing (and printing) of these materials by a procedure customary perse, in which a compound of the general formula (1) is used as a colorantand the compound of the general formula (1) is applied to the materialin aqueous medium and fixed in the heat or by means of an alkalinecompound or by means of both.

The dyes of the formula (1) are distinguished by high reactivity, goodfixation properties and very good build-up properties. They cantherefore be used in the exhaust method at low dyeing temperatures andrequire only short steaming times in the pad-steam process. The degreesof fixation are high and the unfixed portions can easily be washed off,the difference between the degree of exhaustion and degree of fixationbeing remarkably small, i.e. the soap loss is very small.

The dyes of the formula (1) are also in particular suitable forprinting, in particular on cotton, but also for the printing ofnitrogen-containing fibers, for example of wool or silk or of mixedfabrics which contain wool or silk.

The dyeings and prints on cellulose fiber materials produced by the dyesaccording to the invention have a high color strength and a highstability of the dye/fiber linkage not only in the acidic but also inthe alkaline range, furthermore good light fastness and very good wetfastness properties, such as wash, water, sea water, cross-dyeing andperspiration fastness properties and also good pleating fastness, hotpress fastness and rub fastness.

The examples which follow serve to illustrate the invention. The partsand percentages are by weight, unless stated otherwise. Parts by weightrelate to parts by volume as the kilograin relates to the liter.

The compounds described in these examples by way of their formulae aregiven in the form of the free acids; in general, they are prepared andisolated in the form of their alkali metal salts, such as lithium salts,sodium salts or potassium salts, and are used for dyeing in the form oftheir salts.

Likewise, the starting compounds and components mentioned in theexamples below, in particular the table examples, in the forth of thefree acid can be used in the synthesis as such or in the form of theirsalts, preferably the alkali metal salts.

The absorption maxima (λ_(max)) in the visible region shown for thecompounds according to the invention were determined, using their alkalimetal salts in aqueous solution. In the table examples, the λ_(max)values are written in brackets next to their hues; the wavelengthnumbers are given in nm.

EXAMPLE 1

4.25 parts of cyanamide are added to a finely divided suspension of 19parts of cyanuric chloride in 200 parts of ice water, the mixture isbrought to a pH of 8.5 to 9 with sodium hydroxide solution andsubsequently stirred for about 1 hour at 0° to 3° C. and a pH of 8.5.After the condensation reaction is completed (which can be checked bythin layer chromatography), the resulting solution is brought to a pH of5 with hydrochloric acid. 23.9 parts of4-hydroxy-7-aminonaphthalene-2-sulfonic acid are added, and the mixtureis stirred for another 2 hours at 20° C. and a pH of 3 to 3.5. Asulfuric acid aqueous suspension prepared in the usual manner (about 320parts) of the diazonium salt of 41.1 parts of2-amino-8-(β-sulfatoethylsulfonyl)naphthalene-6-sulfonic acid is thenadded, and the coupling reaction is carried out at a temperature of 10°to 25° C. and a pH of 6 to 6.5. After adjusting the pH to a value of 5.5and adding kieselguhr, the synthesis solution is clarified at 40° to 50°C. by filtration, and the filtrate is evaporated to dryness at 50° C.under reduced pressure.

This gives a red electrolyte-containing powder of the alkali metal salt(sodium salt) according to the invention of the compound of the formula##STR28##

The compound according to the invention has very good fiber-reactive dyeproperties and dyes the materials mentioned in the description such as,in particular, cellulose fiber materials, for example cotton, by theapplication and fixation processes customary in the art forfiber-reactive dyes, in brilliant orange shades which have high colorstrength and good fastness properties, of which their good water, wash,perspiration, hypochlorite bleaching and hot-press fastness propertiesmay be mentioned in particular.

EXAMPLE 2

31.9 parts of 4-hydroxy-5-aminonaphthalene-2,7-disulfonic acid are addedto a finely divided suspension of 19 parts of cyanuric chloride in 200parts of ice water, and the condensation reaction is first carried outat 0° to 5° C. and a pH of 1.8 to 2.2 for about 3 hours and then at 0°to 20° C. and a pH of 4.5 for about 1 hour. 4.25 parts of cyanamide arethen added, the pH is brought to 10 with aqueous sodium hydroxidesolution, the mixture is slowly heated to 50° to 60° C. and stirred atthis temperature and a pH of 9.5 to 10 for another 2 hours, until thereaction is complete. The pH is then brought to 5 with hydrochloricacid, a sulfuric acid aqueous suspension prepared in the usual manner(about 340 parts) of the diazonium sodium salt of 28.1 parts of4-(α-sulfatoethylsulfonyl)aniline is added, and the coupling reaction iscarried out at 10° to 15° C. and a pH of 4.5. Kieselguhr is then addedto the synthesis solution, the mixture is heated to 40° to 50° C., thepH is brought to 5.5, the mixture is filtered, and the azo compoundaccording to the invention is isolated by evaporating the filtrate underreduced pressure.

The azo compound according to the invention isolated as the alkali metalsalt (sodium salt) has, written in the form of the free acid, theformula ##STR29##

It produces, for example on cotton, by the application and fixationprocesses customary in the art for fiber-reactive dyes red dyeings andprints which have good fastness properties, of which in particular theirgood wash, perspiration, water and hot-press fastness properties may bementioned.

EXAMPLE 3

66.1 parts of3-[1'-sulfo-6'-(β-hydroxyethylsulfonyl)-2'-naphthylazo]-4-hydroxy-5-aminonaphthalene-2,7-disulfonicacid are reacted in aqueous solution at a temperature of 0° to 5° C. anda pH of 4 with 19 parts of cyanuric chloride. 4.3 parts of cyanamide arethen added, and the second condensation reaction is carried out whilesteadily increasing the pH to 10 by means of aqueous sodium hydroxidesolution and the temperature to 50° to 60° C. and subsequently at thistemperature and a pH of 9.5 to 10 for about 2 hours. The azo compoundformed, which contains the β-hydroxyethylsulfonyl group, is salted outfrom the synthesis solution at a pH of 7 by means of potassium chloride,isolated and dried.

10 parts of the product obtained, which contains about 70% of the azocompound, are stirred into 20 parts of 100% sulfuric acid at 5° to 10°C. After the azo compound is completely dissolved, the mixture is pouredonto 80 parts of ice, neutralized with calcium carbonate, filtered offfrom the calcium sulfate with suction, the residue is washed with water,and the filtrate is evaporated to dryness under reduced pressure.

The azo compound according to the invention, which is obtained as thealkali metal salt and has the formula (written in the form of the freeacid) ##STR30## dyes the materials mentioned in the description, suchas, in particular, cotton, by the application processes customary in theart for fiber-reactive dyes in brilliant bluish red shades which havehigh color strength and good fastness properties, of which in particularthe good daylight fastness and good hot-press fastness may be mentioned.

EXAMPLES 4 TO 56

Further azo dyes according to the invention of a general formula (A)##STR31## are described in the table examples below by means of theformula radicals of the general formula (A). They can be preparedaccording to the invention, for example analogously to the aboveexemplary embodiments, using the starting components shown in thegeneral formula (A) (for example the diazo component D--NH₂, thecoupling component H--K--NHR, cyanuric chloride and cyanamide). Theyhave very good fiber-reactive dye properties and dye the materialsmentioned in the description, such as, in particular, cellulose fibermaterials, for example cotton, by the application and fixation processescustomary in the art for fiber-reactive dyes, in the hues shown in theparticular table example (in this case also cotton) which have highcolor strength and good fastness properties.

    ______________________________________                                        Ex.   Radical D--      Radical --K--N(R)--                                                                        Hue                                       ______________________________________                                         4    4-(β-sulfatoethyl-                                                                        3-amino-4-sulfo-                                                                           golden                                          sulfonyl)phenyl  1,6-phenylene-                                                                             yellow                                                           amino                                                   5    3-(β-sulfatoethyl-                                                                        3-amino-4-sulfo-                                                                           golden                                          sulfonyl)phenyl  1,6-phenylene-                                                                             yellow                                                           amino                                                   6    6-(β-sulfatoethyl-                                                                        3-amino-4-sulfo-                                                                           golden                                          sulfonyl)-1-sulfo-                                                                             1,6-phenylene-                                                                             yellow                                          naphth-2-yl      amino                                                   7    2-sulfo-4-(β-sulfato-                                                                     3-amino-4-sulfo-                                                                           golden                                          ethylsulfonyl)phenyl                                                                           1,6-phenylene-                                                                             yellow                                                           amino                                                   8    8-(β-sulfatoethyl-                                                                        3-amino-4-sulfo-                                                                           golden                                          sulfonyl)-6-sulfo-                                                                             1,6-phenylene-                                                                             yellow                                          naphth-2-yl      amino                                                   9    8-(β-sulfatoethyl-                                                                        3-ureido-1,4-                                                                              reddish                                         sulfonyl)-6-sulfo-                                                                             phenyleneamino                                                                             yellow                                          naphth-2-yl                                                             10    8-(β-sulfatoethyl-                                                                        3-acetylamino-                                                                             reddish                                         sulfonyl)-6-sulfo-                                                                             1,4-phenylene-                                                                             yellow                                          naphth-2-yl      amino                                                  11    8-(β-sulfatoethyl-                                                                        3-methyl-1,4-                                                                              reddish                                         sulfonyl)-6-sulfo-                                                                             phenyleneamino                                                                             yellow                                          naphth-2-yl                                                             12    6-(β-sulfatoethyl-                                                                        3-methyl-1,4-                                                                              reddish                                         sulfonyl)-1-sulfo-                                                                             phenyleneamino                                                                             yellow                                          naphth-2-yl                                                             13    6-(β-sulfatoethyl-                                                                        3-acetylamino-                                                                             reddish                                         sulfonyl)-1-sulfo-                                                                             1,4-phenylene-                                                                             yellow                                          naphth-2-yl      amino                                                  14    6-(β-sulfatoethyl-                                                                        3-ureido-1,4-                                                                              reddish                                         sulfonyl)-1-sulfo-                                                                             phenyleneamino                                                                             yellow                                          naphth-2-yl                                                             15    6-vinylsulfonyl-1-                                                                             3-acetylamino-                                                                             reddish                                         sulfonaphth-2-yl 1,4-phenylene-                                                                             yellow                                                           amino                                                  16    4-(β-sulfatoethyl-                                                                        1-[2'-sulfo- yellow                                          sulfonyl)phenyl  1',4'-phenylene-                                                              4'-amino]-3-car-                                                              boxypyrazol-5-on-                                                             4-yl                                                   17    2-sulfo-4-(β-sulfato-                                                                     1-[2'-sulfo- yellow                                          ethylsulfonyl)phenyl                                                                           1',4' -phenylene-                                                             4'-amino]-3-car-                                                              boxypyrazol-5-on-                                                             4-yl                                                   18    6-(β-sulfatoethyl-                                                                        1-[2'-sulfo- yellow                                          sulfonyl)-1-sulfo-                                                                             1',4'-phenylene-                                             naphth-2-yl      4'-amino]-3-car-                                                              boxypyrazol-5-on-                                                             4-yl                                                   19    8-(β-sulfatoethyl-                                                                        1-[2'-sulfo- yellow                                          sulfonyl)-6-sulfo-                                                                             1',4'-phenylene-                                             naphth-2-yl      4'-amino]-3-car-                                                              boxypyrazol-5-on-                                                             4-yl                                                   20    2-methoxy-4-(β-sulfato-                                                                   1-[2'-sulfo- yellow                                          ethylsulfonyl)-5-                                                                              1',4'-phenylene-                                             methylphenyl     4'-amino]-3-car-                                                              boxypyrazol-5-on-                                                             4-yl                                                   21    2,5-dimethoxy-4-(β-                                                                       1-[2'-sulfo- golden                                          sulfatoethylsulfonyl)-                                                                         1',4'-phenylene-                                                                           yellow                                          phenyl           4'-amino]-3-car-                                                              boxypyrazol-5-on-                                                             4-yl                                                   22    4-N-[3'-(β-sulfatoethyl-                                                                  1-[2'-sulfo- yellow                                          sulfonyl)phenyl]amido-                                                                         1',4'-phenylene-                                             carbonylphenyl   4'-amino]-3-car-                                                              boxypyrazol-5-on-                                                             4-yl                                                   23    1:1 copper complex of:        yellowish                                       2-hydroxy-6-(β-sulfato-                                                                   1-[2'-sulfo- brown                                           ethylsulfonyl)phenyl                                                                           1',4'-phenylene-                                                              4'-amino]-3-car-                                                              boxypyrazol-5-on-                                                             4-yl                                                   24    4-(β-sulfatoethyl-                                                                        1-[2'-sulfo- yellow                                          sulfonyl)phenyl  1',4'-phenylene-                                                              4'-amino]-3-                                                                  methylpyrazol-                                                                5-on-4-yl                                              25    2,5-dimethoxy-4-(β-                                                                       1-[2'-sulfo- golden                                          sulfatoethylsulfonyl)-                                                                         1',4'-phenylene-                                                                           yellow                                          phenyl           4' -amino]-3-                                                                 methylpyrazol-                                                                5-on-4-yl                                              26    1:1 copper complex of:                                                                         1-[2'-sulfo- yellowish                                       2-hydroxy-5-(β-sulfato-                                                                   1',4'-phenylene-                                                                           brown                                           ethylsulfonyl)phenyl                                                                           4'-amino]-3-                                                                  methylpyrazol-                                                                5-on-4-yl                                              27    4-(β-sulfatoethyl-                                                                        4-hydroxy-2- orange                                          sulfonyl)phenyl  sulfo-3,6-                                                                    naphthylene-6-                                                                amino                                                  28    3-(β-sulfatoethyl-                                                                        4-hydroxy-2- orange                                          sulfonyl)phenyl  sulfo-3,6-                                                                    naphthylene-6-                                                                amino                                                  29    4-methoxy-3-(β-sulfato-                                                                   4-hydroxy-2- red                                             ethylsulfonyl)phenyl                                                                           sulfo-3,6-                                                                    naphthylene-6-                                                                amino                                                  30    2-methoxy-5-(β-sulfato                                                                    4-hydroxy-2- red                                             ethylsulfonyl)phenyl-                                                                          sulfo-3,6-                                                                    naphthylene-6-                                                                amino                                                  31    4-(β-sulfatoethyl-                                                                        4-hydroxy-2- orange                                          sulfonyl)phenyl  sulfo-3,7-                                                                    naphthylene-7-                                                                amino                                                  32    6-(β-sulfatoethyl-                                                                        4-hydroxy-2- orange                                          sulfonyl)-1-sulfo-                                                                             sulfo-3,7-                                                   naphth-2-yl      naphthylene-7-                                                                amino                                                  33    8-(β-sulfatoethyl-                                                                        4-hydroxy-2- orange                                          sulfonyl)-6-sulfo-                                                                             sulfo-3,7-                                                   naphth-2-yl      naphthylene-7-                                                                amino                                                  34    4-methoxy-3-(β-sulfato-                                                                   4-hydroxy-2- scarlet                                         ethylsulfonyl)phenyl                                                                           sulfo-3,7-                                                                    naphthylene-7-                                                                amino                                                  35    2-methoxy-5-(β-sulfato-                                                                   4-hydroxy-2- scarlet                                         ethylsulfonyl)phenyl                                                                           sulfo-3,7-                                                                    naphthylene-7-                                                                amino                                                  36    2-sulfo-4-(β-sulfato-                                                                     4-hydroxy-2- orange                                          ethylsulfonyl)phenyl                                                                           sulfo-3,7-                                                                    naphthylene-7-                                                                amino                                                  37    1:1 copper complex of:                                                                         4-hydroxy-2- ruby                                            2-hydroxy-5-(β-sulfato-                                                                   sulfo-3,7-                                                   ethylsulfonyl)phenyl                                                                           naphthylene-7-                                                                amino                                                  38    4-(β-sulfatoethyl-                                                                        4-hydroxy-2,8-                                                                             yellowish                                       sulfonyl)phenyl  disulfo-3,5- red                                                              naphthylene-5-                                                                amino                                                  39    3-(β-sulfatoethyl-                                                                        4-hydroxy-2,7-                                                                             red                                             sulfonyl)phenyl  disulfo-3,5-                                                                  naphthylene-5-                                                                amino                                                  40    2-sulfo-4-(β-sulfato-                                                                     4-hydroxy-2,7-                                                                             yellowish                                       ethylsulfonyl)phenyl                                                                           disulfo-3,5- red                                                              naphthylene-5-                                                                amino                                                  41    4-N-[3'-(β-sulfatoethyl-                                                                  4-hydroxy-2,7-                                                                             red                                             sulfonyl)phenyl]amido                                                                          disulfo-3,5-                                                 carbonylphenyl   naphthylene-5-                                                                amino                                                  42    2-methoxy-5-(β-sulfato-                                                                   4-hydroxy-2,7-                                                                             bluish                                          ethylsulfonyl)phenyl                                                                           disulfo-3,5- red                                                              naphthylene-5-                                                                amino                                                  43    8-(β-sulfatoethylsul-                                                                     4-hydroxy-2,7-                                                                             bluish                                          fonyl)naphth-2-yl                                                                              disulfo-3,5- red                                                              naphthylene-5-                                                                amino                                                  44    6-(β-sulfatoethylsul-                                                                     4-hydroxy-2,7-                                                                             bluish                                          fonyl)-1-sulfonaphth-                                                                          disulfo-3,5- red                                             2-yl             naphthylene-5-                                                                amino                                                  45    8-(β-sulfatoethylsul-                                                                     4-hydroxy-2,7-                                                                             bluish                                          fonyl)-6-sulfonaphth-                                                                          disulfo-3,5- red                                             2-yl             naphthylene-5-                                                                amino                                                  46    1:1 copper comlex of:                                                                          4-hydroxy-2,7-                                                                             violet                                          2-hydroxy-4-(β-sulfato-                                                                   disulfo-3,5-                                                 ethylsulfonyl)phenyl                                                                           naphthylene-5-                                                                amino                                                  47    1:1 copper complex of:                                                                         4-hydroxy-2,7-                                                                             blue                                            2-hydroxy-4-(β-sulfato-                                                                   disulfo-3,5-                                                 ethylsulfonyl)-5-methoxy-                                                                      naphthylene-5-                                               phenyl           amino                                                  48    1:1 copper complex of:                                                                         4-hydroxy-2,7-                                                                             blue                                            8-(β-sulfatoethylsul-                                                                     disulfo-3,5-                                                 fonyl)-6-sulfo-1-                                                                              naphthylene-5-                                               hydroxynaphth-2-yl                                                                             amino                                                  49    1:1 copper complex of:                                                                         4-hydroxy-2,7-                                                                             dark                                            3-[2'-hydroxy-5'-(β-                                                                      disulfo-3,5- blue                                            sulfatoethylsulfonyl)-                                                                         naphthylene-5-                                               phenylazo]-2-sulfo-4-                                                                          amino                                                        hydroxynapht-7-yl [sic]                                                 50    3-sulfo-4-[3'-(β-sul-                                                                     4-hydroxy-2,7-                                                                             blue                                            fatoethylsulfonyl)-                                                                            disulfo-3,5-                                                 phenylamino]phenyl                                                                             naphthylene-5-                                                                amino                                                  51    3-sulfo-4-[2'-methoxy-                                                                         4-hydroxy-2,7-                                                                             blue                                            5'-(β-sulfatoethyl-                                                                       disulfo-3,5-                                                 sulfonyl)phenylamino]-                                                                         naphthylene-5-                                               phenyl           amino                                                  52    6-sulfo-4-[3'-(β-sul-                                                                     6-sulfo-1,2- brown                                           fatoethylsulfonyl)-4'-                                                                         naphthylene-1-                                               methoxyphenylazo]-                                                                             amino                                                        naphth-1-yl                                                             53    6-sulfo-4-[1'-sulfo-                                                                           3-methyl-1,4-                                                                              brown                                           6'-(β-sulfatoethyl-                                                                       phenylene-1-                                                 sulfonyl)-naphth-2'-                                                                           amino                                                        ylazo]-naphth-1-yl                                                      54    1:2 chromium complex of:                                                                       2,7-disulfo-4-                                                                             navy                                            2-hydroxy-5-(β-sulfato-                                                                   hydroxy-3,5-                                                 ethylsulfonyl)phenyl                                                                           naphthylene-5-                                                                amino                                                  55    1:2 cobalt complex of:                                                                         2,7-disulfo-4-                                                                             violet                                          2-hydroxy-5-(β-sulfato-                                                                   hydroxy-3,5-                                                 ethylsulfonyl)phenyl                                                                           naphthylene-5-                                                                amino                                                  56    1:2 chromium complex of:                                                                       2-sulfo-4-   reddish                                         2-carboxyphenyl  hydroxy-3,7- brown                                                            naphthylene-                                                                  7-amino                                                ______________________________________                                    

EXAMPLE 57

19 parts of cyanuric chloride are dispersed in 200 parts of ice water,and 18.8 parts of 1,3-diaminobenzene-4-sulfonic acid are added. Themixture is initially stirred at 0° to 5° C. and a pH of 2.5 for twohours and then at 0° to 5° C. and a pH of 4 for 30 minutes, and 4.25parts of cyanamide are then added. The pH is brought to 10 by means ofaqueous sodium hydroxide solution, the mixture is gradually heated to50° to 60° C., stirred in this temperature range and at this pH forabout 90 minutes, and then brought to a pH of 7 by means of hydrochloricacid. The 2-sulfo-5-(2'-chloro-4'-cyanamido-s-triazin-6-yl)aminoanilinecompound thus obtained is diazotized directly in its synthesis solutionin the usual manner by first adding 20 parts by volume of an aqueous 5Nsodium nitrite solution and adding the mixture slowly to a mixture of 50parts by volume of aqueous concentrated hydrochloric acid and 600 partsof ice. Stirring is continued for 2 hours, excess nitrous acid isdestroyed, if necessary, by means of sulfamic acid, and the diazoniumsalt suspension obtained is then added to an aqueous solution of 36.2parts of 1-[4'-(β-sulfatoethylsulfonyl)phenyl]-3-methyl-5-pyrazolone;the coupling reaction is carried out at 15° to 25° C. and a pH of 4.5 to5.5, and the synthesis solution is then clarified at 40° to 50° C. bymeans of kieselguhr and filtration.

The azo compound according to the invention of the formula (written inthe form of the free acid) ##STR32## is isolated as its alkali metalsalt (sodium salt) by spray-drying of the filtrate. It has very goodfiber-reactive dye properties and dyes, for example, cotton in strongyellow shades which have good fastness properties, of which inparticular the good daylight fastness and the good perspiration fastnesscan be mentioned.

EXAMPLE 58

In accordance with the procedure described in Example 57, 19 parts ofcyanuric chloride are reacted with 18.8 parts of1,3-diaminobenzene-4-sulfonic acid and then with 4.4 parts of cyanamide,this condensation product is diazotized, the diazonium salt suspensionobtained added to an aqueous solution of 60 parts of4-hydroxy-5-amino-6-[4'-(β-sulfatoethylsulfonyl)phenylazo]naphthalene-2,7-disulfonicacid, and the coupling reaction is carried out at 15° to 25° C. and a pHof 4.5 to 5.5. The synthesis solution is clarified by means ofkieselguhr and filtration, and the filtrate is evaporated to drynessunder reduced pressure.

This gives a black electrolyte-containing powder of the alkali metalsalt (sodium salt) of the azo compound according to the invention of theformula (written in the forth of the free acid) ##STR33## The azocompound according to the invention has very good fiber-reactive dyeproperties and dyes the materials mentioned in the description, inparticular cellulose fiber materials, such as cotton, by the applicationprocesses customary for fiber-reactive dyes in navy hues of high colorstrength.

EXAMPLES 59 TO 69

Further azo dyes according to the invention of the general formula (B)##STR34## are described in the table examples below by means of theformula radicals of the general formula (B). They can be preparedaccording to the invention, for example analogously to the aboveexemplary embodiments 57 and using the starting components shown in thegeneral formula (B) (for example the phenylenediamine of the formula H₂N--D--NH₂, the coupling component H--K, cyanuric chloride andcyanamide). They have very good fiber-reactive dye properties and dyethe materials mentioned in the description, such as, in particular,cellulose fiber materials, for example cotton, by the application andfixation processes customary in the art for fiber reactive dyes, in thehues shown in the particular table example (in this case also cotton)which have high color strength and good fastness properties.

    ______________________________________                                        Ex.  Radical D      Radical K        Hue                                      ______________________________________                                        59                                                                                  ##STR35##     1-[2'-sulfo-4'-(β- sulfatoethylsulfonyl)-                                phenyl]-3-methylpyra- zol-5-on-4-yl                                                            yellow                                   60   "              1-[4'-(β-sulfato-                                                                         yellow                                                       ethylsulfonyl)phenyl]-                                                        3-carboxypyrazol-5-on-                                                        4-yl                                                      61   "              1-[2'-sulfo-4'-(β-                                                                        yellow                                                       sulfatoethylsulfonyl)-                                                        phenyl]-3-carbomethoxy-                                                       5-on-4-yl                                                 62   4,6-disulfo-1,3-                                                                             1-[4'-(β-sulfato-                                                                         yellow                                        phenylene      ethylsulfonyl)-                                                               phenyl]-3-methyl-                                                             pyrazol-5-on-4-yl                                         63   4,6-disulfo-1,3-                                                                             1-[4'-(β-sulfato-                                                                         yellow                                        phenylene      ethylsulfonyl)-                                                               phenyl]-3-carbomethoxy-                                                       pyrazol-5-on-4-yl                                         64                                                                                  ##STR36##     1-[4'-(β-sulfato- ethylsulfonyl)phenyl]-                                 3-carboxypyrazol-5- on-4-yl                                                                    yellow                                   65                                                                                  ##STR37##     4-hydroxy-6-[N- methyl-N-(β-sulfato- ethylsulfony                        l)amino]- 2-sulfonaphth-3-yl                                                                   orange                                   66   "              4-hydroxy-7-[N-  orange                                                       methyl-N-(β-sulfato-                                                     ethylsulfonyl)amino]-                                                         2-sulfonaphth-3-yl                                        67   "              4-hydroxy-5-amino-6-                                                                           navy                                                         [4'-(β-sulfatoethyl-                                                     sulfonyl)-phenylazo]-                                                         2,7-disulfonaphth-3-yl                                    68   "              4-hydroxy-5-amino-6-                                                                           navy                                                         [2'-bromo-4'-(β-                                                         sulfatoethyl-sul-                                                             fonyl)-phenylazo]-                                                            2,7-disulfonaphth-                                                            3-yl                                                      69   "              4-hydroxy-5-amino-6-                                                                           navy                                                         [2'-methoxy-5'-(β-                                                       sulfatoethylsul-                                                              fonyl)phenylazo]-2,7-                                                         disulfonaphth-3-yl                                        ______________________________________                                    

We claim:
 1. A water-soluble azo dye of the general formula (4)##STR38## in which Y is vinyl, β-sulfatoethyl, β-thiosulfatoethyl,β-phosphatoethyl, β-alkanoyloxyethyl of 2 to 5 carbon atoms in thealkanoyl radical, β-benzoyloxyethyl, β-(sulfobenzyoxyloxy)ethyl,β-(p-toluenesulfonyloxy)ethyl or β-halogenoethyl;P is the number 1 or 2M is hydrogen or an alkali metal, R¹ is hydrogen, alkyl of 1 to 4 carbonatoms, alkoxy of 1 to 4 carbon atoms, halogen, trifluoromethyl, carboxylor sulfo, R² is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4carbon atoms, halogen or sulfo, D¹ is a benzene or naphthalene ring andZ¹ is a group of the general formula (3a) ##STR39## in which X ischlorine, bromine, sulfo, alkoxysulfonyl of 1 to 4 carbon atoms orphenylsulfonyl.
 2. A water-soluble azo dye of the general formula (9)##STR40## in which Y is vinyl, β-sulfatoethyl, β-thiosulfatoethyl,β-phosphatoethyl, β-alkanoyloxyethyl of 2 to 5 carbon atoms in thealkanoyl radical, β-benzoyloxyethyl, β-(sulfobenzyoxyloxy)ethyl,β-(p-toluenesulfonyloxy)ethyl or β-halogenoethyl;P is the number 1 or 2,M is hydrogen or an alkali metal, m is the number zero, 1 or 2, R¹ ishydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms,halogen, trifluoromethyl, carboxyl or sulfo, R² is hydrogen, alkyl of 1to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, halogen or sulfo, D¹is a benzene or naphthalene ring and Z¹ is a group of the generalformula (3a) ##STR41## in which X is chlorine, bromine, sulfo,alkoxysulfonyl of 1 to 4 carbon atoms or phenylsulfonyl.
 3. Awater-soluble azo dye of the general formula (4a) ##STR42## in which Yis vinyl, β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl,β-alkanoyloxyethyl of 2 to 5 carbon atoms in the alkanoyl radical,β-benzoyloxyethyl, β-(sulfobenzyoxyloxy)ethyl,β-(p-toluenesulfonyloxy)ethyl or β-halogenoethyl;P is the number 1 or 2M is hydrogen or an alkali metal, R¹ is hydrogen, alkyl of 1 to 4 carbonatoms, alkoxy of 1 to 4 carbon atoms, halogen, trifluoromethyl, carboxylor sulfo, R² is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4carbon atoms, halogen or sulfo, D¹ is a benzene or naphthalene ring andZ¹ is a group of the general formula (3a) ##STR43## in which X ischlorine, bromine, sulfo, alkoxysulfonyl of 1 to 4 carbon atoms orphenylsulfonyl.
 4. A dye as claimed in claim 1 wherein X is chlorine. 5.A dye as claimed in claim 2, wherein X is chlorine.
 6. A dye as claimedin claim 3, wherein X is chlorine.
 7. A dye as claimed in claim 1,wherein Y is vinyl or β-sulfatoethyl.
 8. A dye as claimed in claim 2,wherein Y is vinyl or β-sulfatoethyl.
 9. A dye as claimed in claim 3,wherein Y is vinyl or β-sulfatoethyl.
 10. A process for dyeing ofhydroxyl- and or carboxamido-containing material in which a dye isapplied to or incorporated in the material and fixed by means of heatand/or may means of an alkaline agent, wherein the dye used is acompound as claimed in one of claims 1, 2 and
 3. 11. A process fordyeing a material containing hydroxy or carboxamide groups, comprisingapplying a dye as claimed in claim 1, to the material and fixing it by ameans of heat or by a means of alkaline agent or by both.
 12. A processfor dyeing a material containing hydroxy or carboxamide groups,comprising applying a dye as claimed in claim 2, to the material andfixing it by a means of heat or by a means of alkaline agent or by both.13. A process for dyeing a material containing hydroxy or carboxamidegroups, comprising applying a dye as claimed in claim 3, to the materialand fixing it by a means of heat or by a means of alkaline agent or byboth.
 14. The process as claimed in claim 11, wherein said material is afiber material.
 15. The process as claimed in claim 12, wherein saidmaterial is a fiber material.
 16. The process as claimed in claim 13,wherein said material is a fiber material.